Category: publications

Jul 27 2018

Book chapter: Computational Chemistry Experiment Possibilities

Authors: Bartłomiej M. Szyja and Danny Vanpoucke
Book: Zeolites and Metal-Organic Frameworks, (2018)
Chapter Ch 9, p 235-264
Title Computational Chemistry Experiment Possibilities
ISBN: 978-94-629-8556-8
export: bibtex
pdf: <Amsterdam University Press>
<Open Access>

 

Zeolites and Metal-Organic Frameworks (the hard-copy)

Abstract

Thanks to a rapid increase in the computational power of modern CPUs, computational methods have become a standard tool for the investigation of physico-chemical phenomena in many areas of chemistry and technology. The area of porous frameworks, such as zeolites, metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs), is not different. Computer simulations make it possible, not only to verify the results of the experiments, but even to predict previously inexistent materials that will present the desired experimental properties. Furthermore, computational research of materials provides the tools necessary to obtain fundamental insight into details that are often not accessible to physical experiments.

The methodology used in these simulations is quite specific because of the special character of the materials themselves. However, within the field of porous frameworks, density functional theory (DFT) and force fields (FF)
are the main actors. These methods form the basis of most computational studies, since they allow the evaluation of the potential energy surface (PES) of the system.

Related:

Newsflash: here

Oct 26 2017

Audioslides tryout.

One of the new features provided by Elsevier upon publication is the creation of audioslides. This is a kind of short presentation of the publication by one of the authors. I have been itching to try this since our publication on the neutral C-vancancy was published. The interface is quite intuitive, although the adobe flash tend to have a hard time finding the microphone. However, once it succeeds, things go quite smoothly. The resolution of the slides is a bit low, which is unfortunate (but this is only for the small-scale version, the large-scale version is quite nice as you can see in the link below). Maybe I’ll make a high resolution version video and put it on Youtube, later.

The result is available here (since the embedding doesn’t play nicely with WP).

And a video version can be found here.
 

Sep 23 2017

Revisiting the Neutral C-Vacancy in Diamond: Localization of Electrons through DFT+U

Authors: Danny E. P. Vanpoucke and Ken Haenen
Journal: Diam. Relat. Mater 79, 60-69 (2017)
doi: 10.1016/j.diamond.2017.08.009
IF(2017): 2.232
export: bibtex
pdf: <DiamRelatMater>

 

Combining a scan over possible values for U and J with reference electronic structures obtained using the hybrid functional HSE06, DFT+U can be fit to provide hybrid functional quality electronic structures at the cost of DFT calculations.
Graphical Abstract: Combining a scan over possible values for U and J with reference electronic structures obtained using the hybrid functional HSE06, DFT+U can be fit to provide hybrid functional quality electronic structures at the cost of DFT calculations.

Abstract

The neutral C-vacancy is investigated using density functional theory calculations. We show that local functionals, such as PBE, can predict the correct stability order of the different spin states, and that the success of this prediction is related to the accurate description of the local magnetic configuration. Despite the correct prediction of the stability order, the PBE functional still fails predicting the defect states correctly. Introduction of a fraction of exact exchange, as is done in hybrid functionals such as HSE06, remedies this failure, but at a steep computational cost. Since the defect states are strongly localized, the introduction of additional on site Coulomb and exchange interactions, through the DFT+U method, is shown to resolve the failure as well, but at a much lower computational cost. In this work, we present optimized U and J parameters for DFT+U calculations, allowing for the accurate prediction of defect states in defective
diamond. Using the PBE optimized atomic structure and the HSE06 optimized electronic structure as reference, a pair of on-site Coulomb and exchange parameters (U,J) are fitted for DFT+U studies of defects in diamond.

Related:

Poster-presentation: here

DFT+U series (varying J) for a specific spin state of the C-vacancy defect.

DFT+U series (varying J) for a specific spin state of the C-vacancy defect.

Sep 23 2017

A combined experimental and theoretical investigation of the Al-Melamine reactive milling system: a mechanistic study towards AlN-based ceramics

Authors: Seyyed Amin Rounaghi, Danny E.P. Vanpoucke, Hossein Eshghi, Sergio Scudino, Elaheh Esmaeili, Steffen Oswald and Jürgen Eckert
Journal: J. Alloys Compd. 729, 240-248 (2017)
doi: 10.1016/j.jallcom.2017.09.168
IF(2017): 3.779
export: bibtex
pdf: <J.Alloys Compd.>

 

Graphical Abstract: Evolution of the end products as function of Al and N content during ball-milling synthesis of AlN.
Graphical Abstract: Evolution of the end products as function of Al and N content during ball-milling synthesis of AlN.

Abstract

A versatile ball milling process was employed for the synthesis of hexagonal aluminum nitride (h-AlN) through the reaction of metallic aluminum with melamine. A combined experimental and theoretical study was carried out to evaluate the synthesized products. Milling intermediates and products were fully characterized via various techniques including XRD, FTIR, XPS, Raman and TEM. Moreover, a Boltzmann distribution model was proposed to investigate the effect of milling energy and reactant ratios on the thermodynamic stability and the proportion of different milling products. According to the results, the reaction mechanism and milling products were significantly influenced by the reactant ratio. The optimized condition for AlN synthesis was found to be at Al/M molar ratio of 6, where the final products were consisted of nanostructured AlN with average crystallite size of 11 nm and non-crystalline heterogeneous carbon.

Apr 28 2017

Mechanochemical synthesis of nanostructured metal nitrides, carbonitrides and carbon nitride: A combined theoretical and experimental study

Authors: Seyyed Amin Rounaghi, Danny E.P. Vanpoucke, Hossein Eshghi, Sergio Scudino, Elaheh Esmaeili, Steffen Oswald and Jürgen Eckert
Journal: Phys. Chem. Chem. Phys. 19, 12414-12424 (2017)
doi: 10.1039/C7CP00998D
IF(2017): 3.906
export: bibtex
pdf: <Phys.Chem.Chem.Phys.>

Abstract

Nowadays, the development of highly efficient routes for the low cost synthesis of nitrides is greatly growing. Mechanochemical synthesis is one of those promising techniques which is conventionally employed for the synthesis of nitrides by long term milling of metallic elements under pressurized N2 or NH3 atmosphere (A. Calka and J. I. Nikolov, Nanostruct. Mater., 1995, 6, 409-412). In the present study, we describe a versatile, room-temperature and low cost mechanochemical process for the synthesis of nanostructured metal nitrides (MNs), carbonitrides (MCNs) and carbon nitride (CNx). Based on this technique, melamine as a solid nitrogen-containing organic compound (SNCOC) is ball milled with four different metal powders (Al, Ti, Cr and V) to produce nanostructured AlN, TiCxN1-x, CrCxN1-x, and VCxN1-x (x~0.05). Both theoretical and experimental techniques are implemented to determine the reaction intermediates, products, by-products and finally, the mechanism underling this synthetic route. According to the results, melamine is polymerized in the presence of metallic elements at intermediate stages of the milling process, leading to the formation of a carbon nitride network. The CNx phase subsequently reacts with the metallic precursors to form MN, MCN or even MCN-CNx nano-composites depending on the defect formation energy and thermodynamic stability of the corresponding metal nitride, carbide and C/N co-doped structures.

Mar 30 2017

Linker Functionalization in MIL-47(V)-R Metal–Organic Frameworks: Understanding the Electronic Structure

Authors: Danny E. P. Vanpoucke
Journal: J. Phys. Chem. C 121(14), 8014-8022 (2017)
doi: 10.1021/acs.jpcc.7b01491
IF(2017): 4.484
export: bibtex
pdf: <J.Phys.Chem.C>
Graphical Abstract: Evolution of the electronic band structure of MIL-47(V) upon OH-functionalization of the BDC linker.
Graphical Abstract: Evolution of the electronic band structure of MIL-47(V) upon OH-functionalization of the BDC linker. The π-orbital of the BDC linker splits upon functionalisation, and the split-off π-band moves up into the band gap, effectively reducing the latter.

Abstract

Metal–organic frameworks (MOFs) have gained much interest due to their intrinsic tunable nature. In this work, we study how linker functionalization modifies the electronic structure of the host MOF, more specifically, the MIL-47(V)-R (R = −F, −Cl, −Br, −OH, −CH3, −CF3, and −OCH3). It is shown that the presence of a functional group leads to a splitting of the π orbital on the linker. Moreover, the upward shift of the split-off π-band correlates well with the electron-withdrawing/donating nature of the functional groups. For halide functional groups the presence of lone-pair back-donation is corroborated by calculated Hirshfeld-I charges. In the case of the ferromagnetic configuration of the host MIL-47(V+IV) material a half-metal to insulator transition is noted for the −Br, −OCH3, and −OH functional groups, while for the antiferromagnetic configuration only the hydroxy group results in an effective reduction of the band gap.

Sep 25 2016

Mechanochemical route to the synthesis of nanostructured Aluminium nitride

Authors: S. A. Rounaghi, H. Eshghi, S. Scudino, A. Vyalikh, D. E. P. Vanpoucke, W. Gruner,
S. Oswald, A. R. Kiani Rashid, M. Samadi Khoshkhoo, U. Scheler and J. Eckert
Journal: Scientific Reports 6, 33375 (2016)
doi: 10.1038/srep33375
IF(2016): 4.259
export: bibtex
pdf: <Sci.Rep.> (open access)

Abstract

Hexagonal Aluminium nitride (h-AlN) is an important wide-bandgap semiconductor material which is conventionally fabricated by high temperature carbothermal reduction of alumina under toxic ammonia atmosphere. Here we report a simple, low cost and potentially scalable mechanochemical procedure for the green synthesis of nanostructured h-AlN from a powder mixture of Aluminium and melamine precursors. A combination of experimental and theoretical techniques has been employed to provide comprehensive mechanistic insights on the reactivity of melamine, solid state metalorganic interactions and the structural transformation of Al to h-AlN under non-equilibrium ball milling conditions. The results reveal that melamine is adsorbed through the amine groups on the Aluminium surface due to the long-range van der Waals forces. The high energy provided by milling leads to the deammoniation of melamine at the initial stages followed by the polymerization and formation of a carbon nitride network, by the decomposition of the amine groups and, finally, by the subsequent diffusion of nitrogen into the Aluminium structure to form h-AlN

Feb 11 2016

First-Principles Study of Antisite Defect Configurations in ZnGa2O4:Cr Persistent Phosphors

Authors: Arthur De Vos, Kurt Lejaeghere, Danny E. P. Vanpoucke, Jonas J. Joos, Philippe F. Smet, and Karen Hemelsoet
Journal: Inorg. Chem. 55(5), 2402-2412 (2016)
doi: 10.1021/acs.inorgchem.5b02805
IF(2016): 4.857
export: bibtex
pdf: <Inorg.Chem>
Graphical Abstract: (left) Ball-and-stick model of zinc gallate (right) density of states of Cr doped zinc gallate.
Graphical Abstract: First-principles simulations on zinc gallate solid phosphors (ZGO) containing a chromium dopant and antisite defects (left) rationalize the attractive interactions between the various elements. A large number of antisite pair configurations is investigated and compared with isolated antisite defects. Defect energies point out the stability of the antisite defects in ZGO. Local structural distortions are reported, and charge transfer mechanisms are analyzed based on theoretical density of states (right) and Hirshfeld-I charges.

Abstract

Zinc gallate doped with chromium is a recently developed near-infrared emitting persistent phosphor, which is now extensively studied for in vivo bioimaging and security applications. The precise mechanism of this persistent luminescence relies on defects, in particular, on antisite defects and antisite pairs. A theoretical model combining the solid host, the dopant, and/or antisite defects is constructed to elucidate the mutual interactions in these complex materials. Energies of formation as well as dopant, and defect energies are calculated through density-functional theory simulations of large periodic supercells. The calculations support the chromium substitution on the slightly distorted octahedrally coordinated gallium site, and additional energy levels are introduced in the band gap of the host. Antisite pairs are found to be energetically favored over isolated antisites due to significant charge compensation as shown by calculated Hirshfeld-I charges. Significant structural distortions are found around all antisite defects. The local Cr surrounding is mainly distorted due to a ZnGa antisite. The stability analysis reveals that the distance between both antisites dominates the overall stability picture of the material containing the Cr dopant and an antisite pair. The findings are further rationalized using calculated densities of states and Hirshfeld-I charges.

Feb 01 2016

Computational Materials Science: Where Theory Meets Experiments

Authors: Danny E. P. Vanpoucke,
Journal: Developments in Strategic Ceramic Materials:
Ceramic Engineering and Science Proceedings 36(8), 323-334 (2016)
(ICACC 2015 conference proceeding)
Editors: Waltraud M. Kriven, Jingyang Wang, Dongming Zhu,Thomas Fischer, Soshu Kirihara
ISBN: 978-1-119-21173-0
webpage: Wiley-VCH
export: bibtex
pdf: <preprint> 

Abstract

In contemporary materials research, we are able to create and manipulate materials at ever smaller scales: the growth of wires with nanoscale dimensions and the deposition of layers with a thickness of only a few atoms are just two examples that have become common practice. At this small scale, quantum mechanical effects become important, and this is where computational materials research comes into play. Using clever approximations, it is possible to simulate systems with a scale relevant for experiments. The resulting theoretical models provide fundamental insights in the underlying physics and chemistry, essential for advancing modern materials research. As a result, the use of computational experiments is rapidly becoming an important tool in materials research both for predictive modeling of new materials and for gaining fundamental insights in the behavior of existing materials. Computer and lab experiments have complementary limitations and strengths; only by combining them can the deepest fundamental secrets of a material be revealed.

In this paper, we discuss the application of computational materials science for nanowires on semiconductor surfaces, ceramic materials and flexible metal-organic frameworks, and how direct comparison can advance insight in the structure and properties of these materials.

Feb 01 2016

Doping of CeO2 as a Tunable Buffer Layer for Coated Superconductors: A DFT Study of Mechanical and Electronic Properties

Authors: Danny E. P. Vanpoucke,
Journal: Developments in Strategic Ceramic Materials:
Ceramic Engineering and Science Proceedings 36(8), 169-177 (2016)
(ICACC 2015 conference proceeding)
Editors: Waltraud M. Kriven, Jingyang Wang, Dongming Zhu,Thomas Fischer, Soshu Kirihara
ISBN: 978-1-119-21173-0
webpage: Wiley-VCH
export: bibtex
pdf: <preprint> 

Abstract

In layered ceramic superconductor architectures, CeO2 buffer layers are known to form micro cracks during the fabrication process. To prevent this crack formation, doping of the CeO2 layer has been suggested. In this theoretical study, the influence of dopants (both tetravalent and aliovalent) on the mechanical and structural properties of CeO2 is investigated by means of density functional theory. Group IVa and IVb dopants show clearly distinct stability, with the former favouring interface and surface doping, while the latter favour uniform bulk doping. This behaviour is linked to the dopant electronic structure. The presence of charge compensating vacancies is shown to complicate the mechanical and structural picture for aliovalent dopants. We find that the vacancies often counteract the dopant modifications of the host material. In contrast, all dopants show an inverse relation between the bulk modulus and thermal expansion coefficient, independent of their valency and the presence of oxygen vacancies. Based on the study of these idealized systems, new dopants are suggested for applications.